Fire-protection composition and use thereof

ABSTRACT

A composition is described, which contains a binder on the basis of a compound having low-electron multiple carbon bonds and a carbanion-forming compound. By means of the composition according to the invention, coatings having the layer thickness required for the respective fire-resistance duration can be applied in simple and fast manner, wherein the layer thickness can be reduced to a minimum and nevertheless, a good fire-proofing effect can be achieved. The composition according to the invention is particularly suitable for fire-proofing, particularly as a coating for cables and cable runs, to increase their fire-resistance period.

The present invention relates to a composition, particularly acomposition having an ablative effect, a binder on the basis of acompound having low-electron multiple carbon bonds and a compoundforming carbanions, as well as its use for fire protection, particularlyfor coating components such as supports, beams, frame members,insulation systems, for example soft fittings, cables, cable bundles orcable runs to increase the fire-resistance duration.

In fires, cable runs form special danger sites for several reasons. Forone thing, in fires, intensive smoke development occurs from cablesinsulated with plastic, with the emission of harmful, substances, someof them toxic. For another thing, a fire can spread quickly along cableruns, and under some circumstances, can be passed along to a locationfar removed from the original source of the fire. In cable systems, theproblem further exists that in these cables, the effect of theinsulation decreases due to thermal action or burning off, and aninterruption of the electricity flow can occur due to a short-circuit,and thereby the cables are destroyed or become unable to function.

Electrical cables and lines are frequently laid in hallways and dividedinto the adjacent rooms from there. These hallways serve as flight pathsand rescue paths in the event of a fire, which become unusable when afire of cable installation occurs, due to smoke development and toxicfire gases, with burning PVC, for example, releasing severely corrosivegases. Cable concentrations therefore represent a significant hazardpotential, particularly in industrial construction, in power plantsystems, in hospitals, large buildings and administrative buildings,and, in general, in buildings having great installation density. Inthese buildings, cable insulations are often the decisive fire load andcause long-lasting fires with temperatures up to more than 1000° C., inthe most disadvantageous cases. For the reasons stated, particularattention must be paid to cable runs, with regard to fire-protectionmeasures.

In order to prevent these hazards of a lack of ability of the cables tofunction and of the great increase in fire load caused by the cables, atleast for a restricted period of time, it is known to spatially separatethe cables by non-combustible construction materials of constructionmaterial class A1 or A2, in that the cables are laid in installationmaintenance ducts and/or function maintenance ducts, for example.However, this requires great work effort. In addition, a greatrequirement for space occurs, due to complicated designs that must takeinto consideration the weight of the installation maintenance ductsand/or function maintenance ducts in addition to the weight of the cablerun. For this purpose, cables and cable runs are frequently wrapped withinsulation materials such as aluminum oxide silica mats or mineral woolmats. In order to achieve sufficient fire protection, the material mustbe very thick. However, this leads to problems with regard to thedistances between the protected object and adjacent or superimposedobjects. Furthermore, these materials cause problems during normaloperation because of their thermal insulation properties. One of theseproblems is referred to as “reduction in current carrying capacity.”This means that that the heat generated by electrical cables in thecable pipe or the cable run can no longer be conducted away in theregion of the insulation, and this leads to the result that the reliablecurrent operating level permissible in these cables is reduced or thatoverheating of the cables takes place. These disadvantages make thistype of fire protection very inflexible with regard to its area of use.

To prevent these disadvantages, it is also known to apply coatings forprotection of electrical cables, which coatings intumesce, i.e. foam upin the event of a fire, under thermal action, and thereby form aninsulation layer, or absorb heat by means of physical and chemicalprocesses and thereby have a cooling effect.

It is possible, using coatings that form insulation layers, to preventthe involvement of cables in fire events for 30 minutes or longer. Suchcoated cables are often laid in cable runs. In this connection, however,it has been shown that in the case of vertical or inclined placement ofthe cable runs, even a completely foamed-up insulation-layer-formingagent cannot prevent fire from spreading without additional measures. Asthey heat up, the cables deform so greatly between the cable clamps thatthe coating forming the insulation layer tears open and splits off, inpart. Foam that is formed also comes loose from the cables and fallsoff. If the coating is applied after the cables are laid, the cables arenot accessible to their full extent in the region of the clampconstructions. This has the result that in the case of a vertical orinclined placement of the cable runs, only a foam having slightthickness is formed in the event of the fire, in the region of the clampconstruction, which foam is no longer sufficient as fire protection for30 minutes. When laying PVC cables, the problems known in the event of afire therefore occur once again.

It is also known to use halogen-free cables that are treated to beflame-resistant or to have low flammability, which cables areflame-retardant and cause little smoke, and possess only a low capacityfor spreading fire. However, these cables are very expensive and aretherefore used only under conditions of extreme risk.

To avoid the disadvantages of coatings that form insulation layers,materials were applied to the cables and cable holders, in cable runs,which materials demonstrate an ablation effect, i.e. have a coolingeffect under the effect of heat, and form a ceramic, as described, forexample, in DE 196 49 749 A1. In this document, a method for formingfire protection for flammable or heat-endangered components isdescribed, wherein the components are provided with a coating thatcontains an inorganic material composed of finely ground hydraulicbinders such as calcium silicate, calcium aluminate or calcium ferriteas a binder, to which ablative substances such as aluminum hydroxide ormagnesium hydroxide are added. It is a disadvantage of this measure thaton the one hand, application of the material that demonstrates theablation effect is time-intensive, and, on the other hand, adhesion ofthe material to the cables and the cable holders represents a problem.

Other coating systems currently on the market, which do not demonstratesome of the disadvantages mentioned above, are single-component coatingcompositions on the basis of polymer dispersions, which containcompounds that decompose endothermically. A disadvantage of thesecoatings is, for one thing, the relatively long drying period of thecoating and the accompanying low dry layer thickness, since thesesystems dry physically, i.e. by means of evaporation of the solvent.Therefore multiple applications, one following after the other, arerequired for thicker coatings, and this also makes these systemstime-intensive and labor-intensive and therefore uneconomical.

The invention is therefore based on the task of creating a coatingsystem having an ablative effect, of the type stated initially, whichsystem avoids the disadvantages mentioned, is particularly notsolvent-based or water-based, and demonstrates fast hardening, is easyto apply on the basis of correspondingly coordinated viscosity, andrequires only a slight layer thickness on the basis of the high degreeof filling that can be achieved.

This task is accomplished by the composition according to claim 1.Preferred embodiments can be derived from the dependent claims.

Accordingly, an object of the invention is a fire-protection compositionhaving a Constituent A, which contains a multi-functional Michaelacceptor that has at least two low-electron multiple carbon bonds permolecule as functional Michael acceptor groups, having a Constituent B,which contains a multi-functional Michael donor, which has at least twoC,H-acidic bonds per molecule as functional Michael donor groups, havinga Constituent C that contains at least one fire-protection additive thathas an ablative effect, and having a catalyst as Constituent D for theMichael addition reaction. A composition having advantageousfire-protection properties, which has an ablative effect in the event ofa fire and hardens at room temperature, is made available, particularlyfor fire protection of cables, cable bundles or cable runs.

By means of the composition according to the invention, coatings havingthe layer thickness required for the respective fire-resistance durationcan be applied in simple and fast manner. The advantages achieved by theinvention can essentially be seen in that in comparison with the systemson a solvent basis or water basis, with their inherently slow hardeningtimes, the working time can be significantly reduced.

A further advantage lies in that the composition according to theinvention can have a high degree of filling with the fire-protectionadditives, so that a great insulation effect is achieved even with thinlayers. The possible high degree of filling of the composition can beachieved even without the use of volatile solvents. Accordingly, thematerial expenditure decreases, and this has an advantageous effect onmaterial costs, particularly when the composition is applied over largeareas. This is particularly achieved by using a reactive system thatdoes not dry physically, but rather hardens chemically, by way of anaddition reaction. Therefore the compositions do not suffer any volumeloss due to drying of solvents or, in the case of water-based systems,of water. Thus, in a traditional system, a solvent content of about 25%is typical. This means that of a 10 mm wet film layer, only 7.5 mmremain on the substrate to be protected as the actual protective layer.In the case of the composition according to the invention, more than 95%of the coating remains on the substrate to be protected.

In the event of a fire, the binder softens, and the fire-protectionadditives contained in it decompose, as a function of the additivesused, in an endothermic physical or chemical reaction, with theformation of water and inert gases, leading to cooling of the cables,for one thing, and, for another thing, prevents the spread of fire, bymeans of the coating burning off.

The compositions according to the invention demonstrate excellentadhesion to different substrates as compared with solvent-based orwater-based systems, if these are applied without a primer, so that theycan be used universally and adhere not only to the lines to be protectedbut also to other carrier materials.

For a better understanding of the invention, the following explanationsof the terminology used herein are considered to be practical. In thesense of the invention:

-   -   a “Michael addition” is, in general, a reaction between a        Michael donor and a

Michael acceptor, frequently in the presence of a catalyst, such as, forexample, a strong base; Michael addition is sufficiently known andfrequently described in the literature;

-   -   a “Michael acceptor” is a compound having at least one C—C        double bond or C—C triple bond, which is not aromatic and low in        electrons; the Michael acceptor is composed of the functional        Michael acceptor group and a framework;    -   a “functional Michael acceptor group” is the group in the        Michael acceptor that comprises a functional group, more        precisely an electron-withdrawing group, and, in an a position        to this, the C—C double bond or C—C triple bond to which the        Michael donor is added; the low-electron C—C double bond or C—C        triple bond is also referred to as a Michael-active multiple        carbon bond; the functional Michael acceptor group is bound to        the framework or tied into it; a Michael acceptor can have one        or more separate functional Michael acceptor groups; each        functional Michael acceptor group can have a Michael-active        multiple carbon bond; the total number of Michael-active        multiple carbon bonds in the molecule corresponds to the        functionality of the Michael acceptor;    -   a “multi-functional Michael acceptor” is a compound that has two        or more functional Michael acceptor groups or Michael-active        multiple carbon bonds;    -   “low in electrons” means that the multiple carbon bond carries        electron-withdrawing groups in the immediate vicinity, i.e.        generally on the carbon atom adjacent to the multiple bond,        which groups draw off the electron density from the multiple        bond, such as C═O, for example;    -   a “Michael donor” is a C,H-acidic compound, i.e. a compound        having at least one acidic C,H-bond, which can form at least one        carbanion that is able to add to the Michael acceptor; the        acidic hydrogen atom is also referred to as a Michael-active        hydrogen atom; the Michael donor is composed of the functional        Michael donor group and a framework;    -   a “functional Michael donor group” is the group in the Michael        donor that comprises a functional group and, in a position to        it, the carbon atom from which the carbanion is formed; the        functional Michael donor group is bound to the framework; a        Michael donor can have one or more separate functional Michael        donor groups; each functional Michael donor group can have a        Michael-active hydrogen atom; the total number of Michael-active        hydrogen atoms on the molecule corresponds to the functionality        of the Michael donor;    -   a “multi-functional Michael donor” is a compound that has two or        more functional Michael donor groups or Michael-active hydrogen        atoms;    -   the “framework” is part of the donor molecule or acceptor        molecule, to which the functional Michael donor group or the        functional Michael acceptor group is bound;    -   “having an ablative effect” means that when elevated        temperatures, i.e. above 200° C., as they can occur in the event        of a fire, for example, are in effect, a number of chemical and        physical reactions take place, which require energy in the form        of heat, wherein this energy is withdrawn from the surroundings;        this term is used as an equivalent of the term “endothermically        decomposing”;    -   “(meth)acryl . . . / . . . (meth)acryl . . . ” means that both        the “methacryl . . . / . . . methacryl . . . ” and the “acryl .        . . / . . . acryl . . . ” compounds are supposed to be        comprised;    -   an “oligomer” is a molecule having 2 to 5 repetition units, and        a “polymer” is a molecule having 6 or more repetition units, and        they can have structures that are linear, branched, star-shaped,        twisted, hyper-branched or cross-linked; in general, polymers        can have a single type of repetition unit (“homopolymers”) or        they can have more than one type of repetition units        (“copolymers”). As used herein, “resin” is a synonym for        polymer.

In general, it is assumed that the reaction of a Michael donor having afunctionality of two with a Michael acceptor having a functionality oftwo will lead to linear molecular structures. Often, molecularstructures must be produced that are branched and/or cross-linked, andthe use of at least one ingredient having a functionality greater thantwo is required for this. For this reason, the multi-functional Michaeldonor or the multi-functional Michael acceptor or both preferably have afunctionality greater than two.

It is practical if a compound having at least two low-electron multiplecarbon bonds, such as C—C double bonds or C—C triple bonds, preferablyC—C double bonds, per molecule is used as the Michael acceptor, as thefunctional Michael acceptor group.

According to an embodiment of the invention, the Michael acceptor is acompound having at least one functional Michael acceptor group havingthe structure (I) or (II):

in which R¹, R² and R³, independent of one another, in each instance,represent hydrogen or organic radicals, such as, for example, a linear,branched or cyclic, if applicable a substituted alkyl group, aryl group,aralkyl group (also called aryl-substituted alkyl group) or alkarylgroup (also called alkyl-substituted aryl group), including derivativesand substituted versions thereof, wherein these can contain, independentof one another, additional ether groups, carboxyl groups, carbonylgroups, thiol-analogous groups, nitrogen-containing groups orcombinations thereof; X represents oxygen, sulfur or NR⁴, wherein R⁴represents hydrogen or any of the organic groups as described above forR¹, R² and R³; Y represents OR⁵, SR⁵ or NR⁵R⁶, in which R⁵ and R⁶,independent of one another, represent hydrogen or each of the organicgroups as described above for R¹, R² and R³.

Preferably, the functional Michael acceptor group is a group having thestructure (Ill):

in which R¹, R² and R³ are as described above and Y represents OR⁵ orNR⁵R⁶, wherein R⁵ and R⁶ are as described above.

Each functional Michael acceptor group can be directly bound to anotherfunctional Michael acceptor group or a framework by means of one or moreof R¹, R², R³, R⁴, R⁵ or R⁶.

Any C,H-acidic compound that has at least two functional Michael donorgroups and can form carbanions, particularly enolate anions, which canadd to low-electron double bonds in a Michael reaction, can be used as aMichael donor. In this regard, a functional Michael donor group has atleast one acidic CH bond, thereby a difunctional Michael donor, whichcontains two functional Michael donor groups, each of which has anacidic CH bond, has two acidic CH bonds per molecule. A trifunctionalMichael donor can contain three functional Michael donor groups, eachhaving only one acidic CH bond, or it can contain two functional Michaeldonor groups, of which one group contains only one and the second groupcontains two acidic CH bonds. The carbanion is generally released onlyafter the Michael-active hydrogen atom has been split off, by means of asuitable stoichiometrically or catalytically active base.

It is practical if the Michael-active hydrogen atom is bound to a carbonatom that sits between two electron-withdrawing groups, such as, forexample, C═O.

Examples of suitable functional Michael donor groups compriseβ-ketoesters, 1,3-diketones, malonic esters and malonic esterderivatives, such as malonamides, and β-ketoamides (in which theMichael-active hydrogen atom is bound to a carbon atom that sits betweenthe carbonyl groups), cyanoacetate esters and cyanoacetamides (in whichthe Michael-active hydrogen atom is bound to a carbon atom that sitsbetween a carbonyl group and a cyano group), as well as α-nitroalkanes.

Each functional Michael donor group, analogous to the Michael acceptorgroup, can be directly bound to another functional Michael donor groupor a framework.

The multi-functional Michael acceptor and/or the multi-functionalMichael donor of the present invention can have any of a broad pluralityof frameworks, wherein these can be the same or different.

In some embodiments of the present invention, the framework of themulti-functional Michael donor or of the multi-functional Michaelacceptor or of both is a monomer, an oligomer or a polymer.

Preferred frameworks for multi-functional Michael acceptors have amolecular weight (Mw) of 5,000 or less, more preferably of 2,000 orless, and most preferably of 1,000 or less.

Preferred frameworks of the multi-functional Michael donor have amolecular weight (Mw) of 200 or more.

In this regard, the following can be mentioned as examples of polymers:polyalkylene oxide, polyurethane, polyethylene vinyl acetate, polyvinylalcohol, polydiene, hydrogenated polydiene, alkyd, alkyd polyester,(meth)acrylic polymer, polyolefin, polyester, halogenated polyolefin,halogenated polyester, as well as copolymers or mixtures thereof.

In some exemplary embodiments of the invention, one or more polyolcompounds, i.e. one or more multivalent alcohol(s), are used as at leastone framework. Some multivalent alcohols that are suitable as aframework either for the multi-functional Michael acceptor or themulti-functional Michael donor comprise, for example, alkane diols,alkylene glycols, such as ethylene glycol, propylene glycol, glycerols,sugar, pentaerythritols, multivalent derivatives thereof or mixturesthereof. Some examples of multivalent alcohols that are suitable asframeworks are neopentyl glycol, trimethylolpropane, ethylene glycol andpolyethylene glycol, propylene glycol and polypropylene glycol, butanediol, pentane diol, hexane diol, tricyclodecane dimethylol,2,2,4-trimethyl-1,3-pentane diol, Bisphenol A, cyclohexanedimethanol,alkoxylated and/or propoxylated derivatives of neopentyl glycol andtetraethylene glycol cyclohexane dimethanol, hexane diol, castor oil,and trimethylolpropane.

In a preferred embodiment, the Structure (III) is bound to a polyolcompound by way of R⁴, by means of an ester bond, wherein the polyolcompound is as defined above.

Some suitable multi-functional Michael acceptors in the presentinvention comprise, for example, molecules in which some or all theStructures (II) are radicals of (meth)acrylic acid, fumaric acid ormaleic acid, substituted versions or combinations thereof, which arebound to the multi-functional Michael acceptor molecule by way of anester bond. A compound having Structures (II), which comprise two ormore radicals of (meth)acrylic acid, is referred to herein as a“polyfunctional (meth)acrylate”. Polyfunctional (meth)acrylates havingat least two double bonds, which can act as the acceptor in the Michaeladdition, are preferred.

Examples of suitable di(meth)acrylates comprise, but are not restrictedto: ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate,diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate,triethylene glycol di(meth)acrylate, tripropylene glycoldi(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetrapropyleneglycol di(meth)acrylate, polyethylene glycol di(meth)acrylate,polypropylene glycol di(meth)acrylate, mono-ethoxylated ormulti-ethoxylated Bisphenol A di(meth)acrylate, Bisphenol A diglycidylether di(meth)acrylate, resorcinol diglycidyl ether di(meth)acrylate,1,3-propane diol di(meth)acrylate, 1,4-butane diol di(meth)acrylate,1,5-pentane diol di(meth)acrylate, 1,6-hexane diol di(meth)acrylate,neopentyl glycol di(meth)acrylate, cyclohexane dimethanoldi(meth)acrylate, mono-ethoxylated or multi-ethoxylated neopentyl glycoldi(meth)acrylate, mono-propoxylated or multi-propoxylated neopentylglycol di(meth)acrylate, mono-ethoxylated or multi-ethoxylatedcyclohexane dimethanol di(meth)acrylate, propoxylated cyclohexanedimethanol di(meth)acrylate, arylurethane di(meth)acrylates, aliphaticurethane di(meth)acrylate, polyester di(meth)acrylate, and mixturesthereof.

Examples of suitable tri(meth)acrylates comprise, but are not restrictedto: trimethylolpropane tri(meth)acrylate, trifunctional (meth)acrylicacid s triazine, glycerol tri(meth)acrylate, mono-ethoxylated ormulti-ethoxylated trimethylolpropane tri(meth)acrylate,mono-propoxylated or multi-propoxylated trimethylolpropanetri(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate,mono-ethoxylated or multi-ethoxylated glycerol tri(meth)acrylate,mono-propoxylated or multi-propoxylated glycerol tri(meth)acrylate,pentaerythritol tri(meth)acrylate, arylurethane tri(meth)acrylates,aliphatic urethane tri(meth)acrylates, melamine tri(meth)acrylates,epoxy-Novolac tri(meth)acrylates, aliphatic epoxy tri(meth)acrylate,polyester tri(meth)acrylate, and mixtures thereof.

Examples of suitable tetra(meth)acrylates comprise, but are notrestricted to: di(trimethylolpropane) tetra(meth)acrylate,pentaerythritol tetra(meth)acrylate, mono-ethoxylated ormulti-ethoxylated pentaerythritol tetra(meth)acrylate, mono-propoxylatedor multi-propoxylated pentaerythritol tetra(meth)acrylate,dipentaerythritol tetra(meth)acrylate, mono-ethoxylated ormulti-ethoxylated dipentaerythritol tetra(meth)acrylate,mono-propoxylated or multi-propoxylated dipentaerythritoltetra(meth)acrylate, arylurethane tetra(meth)acrylates, aliphaticurethane tetra(meth)acrylates, melamine tetra(meth)acrylates,epoxy-Novolac tetra(meth)acrylates, polyester tetra(meth)acrylates, andmixtures thereof.

Mixtures of the multi-functional (meth)acrylates with one another canalso be used.

Examples of suitable Michael donors comprise: acetoacetates ofmono-ethoxylated and mono-propoxylated or multi-ethoxylated andmulti-propoxylated diols, triols and polyols, ethylene glycoldiacetoacetate, 1,2-propane diol diacetoacetate, 1,3-propane dioldiacetoacetate, 1,4-butane diol diacetoacetate, 1,6-hexane dioldiacetoacetate, neopentyl glycol diacetoacetate, Bisphenol Adiacetoacetate, mono-ethoxylated or multi-ethoxylated Bisphenol Adiacetoacetate, isosorbide diacetoacetate, cyclohexane dimethanoldiacetoacetate, 1,3-benzene dimethanol diacetoacetate (1,3-BDDA),1,4-benzene dimethanol diacetoacetate (1,4-BDDA), trimethylolpropanetriacetoacetate (Lonzamon AATMP), glycerin triacetoacetate,polycaprolactone triacetoacetate, pentaerythritol tetraacetoacetate,dipentaerythritol hexaacetoacetate, glucose triacetoacetate, glucosetetraacetoacetate, glucose pentaacetoacetate, sucrose acetoacetates,sorbitol triacetoacetate, sorbitol tetraacetoacetate, mono-ethoxylatedor multi-ethoxylated neopentyl glycol diacetoacetate, propoxylatedglucose acetoacetatates, propoxylated sorbitol acetoacetates,propoxylated sucrose acetoacetates, polyester acetoacetatates, in whichthe polyester is derived from at least one di-acid and at least onediol, 1,2-ethylene bis-acetoacetamide, polyester amide acetoacetate, inwhich the polyester amide is derived from at least one di-acid and atleast one diamine, acetoacetate-functionalized castor oil, polyesterpolymer, (meth)acrylate polymer.

The Michael donor can be used alone or as a mixture of two or moredifferent compounds.

Depending on the functionality of the Michael acceptor and/or of theMichael donor, the degree of cross-linking of the binder and therebyboth the strength of the resulting coating and its elastic propertiescan be set.

In the composition of the present invention, the relative proportion ofmulti-functional Michael acceptors to multi-functional Michael donorscan be characterized by the reactive equivalent ratio, which is theratio of the number of all functional Michael acceptor groups having theStructures (I), (II) and/or (III) in the composition to the number ofMichael-active hydrogen atoms in the composition. In some embodiments,the reactive equivalent ratio is 0.1 to 10:1; preferably 0.2 to 5:1;more preferably 0.3 to 3:1; most preferably 0.5 to 2:1.

The reaction between the Michael acceptor and the Michael donor takesplace in the presence of a catalyst (Constituent D). The bases usuallyused for Michael-addition reactions, if applicable in combination with asuitable phase transfer catalyst, nucleophile or phosphine, which areknown to a person skilled in the art, can be used as catalysts.Furthermore, quaternary ammonium carbonates and bicarbonates,phosphonium carbonates and bicarbonates can be used as catalysts.

Suitable bases are: tertiary amines such as triethylamine,ethyl-N,N-diisopropylamine, 1,4-diazabicyclo[2.2.2]octane (DABCO);“blocked” bases such as formiate salts of amine or amidine bases;amidine bases such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and1,5-diazabicyclo[4.3.0]non-5-ene (DBN); guanidine bases such astetramethylguanidine (TMG) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene(TBD); inorganic bases such as potassium carbonate, potassiumbicarbonate, phosphates and hydrogen phosphates; quaternary ammoniumhydroxides such as benzyltrimethylammonium hydroxide andtetrabutylammonium hydroxide (TBAH); proton sponge, such as1,8-bis(dimethylamino)naphthalene; pyridine bases such as2,6-di-tert-butylpyridine, 2,6-lutidine, and dimethylaminopyridine(DMAP); carboxylic acid salts such as sodium or potassium salts ofcarboxylic acids, e.g. acetates; alcoholates such as sodium methanolate,potassium methanolate, sodium ethanolate, potassium ethanolate, andpotassium-tert-butyl alcoholate.

Suitable phase transfer catalysts are: quaternary ammonium orphosphonium compounds such as methyltrioctylammonium chloride,benzyltrimethylammonium chloride, hexadecyltributylphosphonium bromide,tetra-n-butylammonium chloride, and tetra-n-butylammonium bromide. Thecatalysis of Michael-addition reactions by means of phase transfercatalysts is described, for example, in E. Diez-Barra, A. de la Hoz, S.Merino, A. Rodriguez, P. Sánchez-Verdú, Tetrahedron 1998, 54, 1835.

Suitable nucleophiles are: primary or secondary alkylamines such asn-pentylamine and di-n-propylamine.

Suitable phosphines are: tertiary phosphines such astri-n-propylphosphine, tri-n-butylphosphine, tri-n-octylphosphine,dimethylphenylphosphine, methyldiphenylphosphine or triphenylphosphine,as described, for example, in J. W. Chan, C. E. Hoyle, A. B. Lowe, M.Bowman, Macromolecules 2010, 43, 6381-6388. In this regard, reference isfurthermore made to WO 2010/030771 A1, the content of which is herebyincorporated into this application.

Suitable quaternary ammonium carbonates or phosphonium carbonates are:tetramethylammonium methyl carbonate, tetramethylammonium ethylcarbonate, tetrabutylammonium methyl carbonate, tetrabutylammonium ethylcarbonate, tetrahexylammonium methyl carbonate, tetrahexylammonium ethylcarbonate, tetraoctylammonium methyl carbonate, tetraoctylammonium ethylcarbonate, tetradecylammonium methyl carbonate, tetradecylammonium ethylcarbonate, hexadecyltrimethylammonium methyl carbonate,hexadecyltrimethylammonium ethyl carbonate, benzyltrimethylammoniummethyl carbonate, benzyltrimethylammonium ethyl carbonate,tetrabutylammonium bicarbonate, tetrahexylammonium bicarbonate,benzyltrimethylammonium bicarbonate, tetrabutylphosphonium methylcarbonate. Such catalysts are described, for example, in M. Fabris, V.Lucchini, M. Noè, A. Perosa, M. Selva, Chem. Eur. J. 2009, 15, 12273 andM. Fabris, M. Noè, A. Perosa, M. Selva, R. Ballini, J. Org. Chem. 2012,77, 1805. In this regard, reference is furthermore made to WO 11124663A, the content of which is hereby incorporated into this application.

The catalyst can be used in catalytic amounts or in equimolar manner orin excess.

Although the reaction of the Michael acceptor and of the Michael donorcan take place in the absence of a solvent, it is sometimes necessary tochange and/or to adapt the effectiveness of the reaction or theviscosity of the constituents, particularly of the Michael acceptor.

Preferably, a solvent is used that has a low viscosity and participatesin the reaction, and is built into the binder, called a reactivediluent. Suitable reactive diluents are themselves Michael acceptorshaving at least one functional Michael acceptor group, which are,however, monomeric or oligomeric, preferably monomeric, and can have thecorresponding frameworks mentioned above.

The method of action of the composition according to the invention,which has an ablative effect, is based on an endothermic physical and/orchemical reaction, wherein substances which require large amounts ofenergy in their decomposition are contained in the composition. If thehardened composition is exposed to an elevated temperature, such as, forexample, in the event of a fire, to the temperature of the fire, anumber of chemical and physical processes are put into motion. Theseprocesses are, for example, release of steam, a change in the chemicalcomposition, and the formation of non-combustible gases, which keep theoxygen required for combustion away from the cable surface. All of theseprocesses require a large amount of energy, which is withdrawn from thefire. After the conversion of all the organic constituents has beenconcluded, a stable insulation layer composed of inorganic constituentshas formed, which has an additional insulating effect.

According to the invention, Constituent C therefore contains at leastone fire-protection additive that has an ablative effect, wherein bothindividual compounds and a mixture of multiple compounds can be used asadditives.

It is practical if materials that form energy-consuming layers by meansof splitting off water, which is embedded in the form of water ofcrystallization, for example, and water evaporation, are used asfire-protection additives having an ablative effect. In this regard, theheat energy that must be expended to split off the water is withdrawnfrom the fire. Furthermore, materials that change chemically, i.e.decompose, evaporate, sublimate or melt in an endothermic reaction underthe effect of heat, are used. As a result, the coated substrates arecooled. Frequently, inert, i.e. non-combustible gases such as carbondioxide, for example, are released during decomposition, and theseadditionally dilute the oxygen in the immediate vicinity of the coatedsubstrate.

Hydroxides such as aluminum hydroxide and magnesium hydroxide, as wellas their hydrates, which split off water, as well as carbonates such ascalcium carbonate, which split off carbon dioxide, are suitable asconstituents that split off gas. Basic carbonates can split off bothwater and CO₂. A combination of constituents that begin splitting offgas at different temperatures is preferred. Thus, in the case ofaluminum hydroxide, splitting off water already begins at approximately200° C., while in the case of magnesium hydroxide, splitting off waterstarts at approximately 350° C., so that splitting off gas takes placeover a greater temperature range.

Suitable materials having an ablative effect are inorganic hydroxides orhydrates that give off water under the effect of heat, such as those ofsodium, potassium, lithium, barium, calcium, magnesium, boron, aluminum,zinc, nickel, furthermore, boric acid and its partially dehydratedderivatives.

The following compounds can be mentioned as examples: LiNO₃.3H₂O,Na₂CO₃H₂O (thermonatrite), Na₂CO₃.7H₂O, Na₂CO₃.10H₂O (soda),Na₂Ca(CO₃)2.2H₂O (pirssonite), Na₂Ca(CO₃)₂.5H₂O (gaylussite),Na(HCO₃)Na₂CO₃.2H₂O (trona), Na₂S₂O₃.5H₂O, Na₂O₃Si.5H₂O, KF.2H₂O,CaBr₂.2H₂O, CaBr₂.6H₂O, CaSO₄.2H₂O (gypsum), Ca(SO₄).½H₂O (bassanite),Ba(OH)₂.8H₂O, Ni(NO₃)₂.6H₂O, Ni(NO₃)₂.4H₂O, Ni(NO₃)₂.2H₂O,Zn(NO₃)₂.4H₂O, Zn(NO₃)₂.6H₂O, (ZnO)₂(B₂O₃)₂.3H₂O, Mg(NO₃)₂.6H₂O (U.S.Pat. No. 5,985,013 A), MgSO₄.7H₂O (EP1069172A), Mg(OH)₂, Al(OH)₃,AI(OH)₃.3H₂O, AlOOH (boehmite), Al₂[SO₄]₃.nH₂O with n=14-18 (U.S. Pat.No. 4,462,831 B), if applicable in a mixture with AlNH₄(SO₄)₂.12H₂O(U.S. Pat. No. 5,104,917A), KAl(SO₄)₂.12H₂O (EP1069172A),CaO.Al₂O₃.10H₂O (nesquehonite), MgCO₃.3H₂O (wermlandite),Ca₂Mg₁₄(Al,Fe)₄CO₃(OH)₄₂.29H₂O (thaumasite), Ca₃Si(OH)₆(SO₄)(CO₃).12H₂O(artinite), Mg₂(OH)₂CO₃.H₂O (ettringite), 3CaO.Al₂O₃.3CaSO₄.32H₂O(hydromagnesite), Mg₅(OH)₂(CO₃)₄.4H₂O (hydrocalumite), Ca₄Al₂(OH)₁₄.6H₂O(hydrotalcite), Mg₆Al₂(OH)₁₆CO₃.4H₂O alumohydrocalcite,CaAl₂(OH)₄(CO₃)₂.3H₂O scarbroite, Al₁₄(CO₃)₃(OH)₃₆ hydrogarnet,3CaO.Al₂O₃.6H₂O dawsonite, NaAl(OH)CO₃, hydrated zeolites, vermiculites,colemanite, perlites, mica, alkali silicates, borax, modified carbonsand graphites, silicic acids.

In a preferred embodiment, the hydrated salts are selected from thegroup consisting of Al₂(SO₄) 16-18H₂O, NH₄Fe(SO₄)₂.12H₂O, Na₂B₄O₇.10H₂O,NaAl(SO₄)₂.12H₂O, AlNH₄(SO₄)₂. 12-24H₂O, Na₂SO₄.10H₂O, MgSO₄.7H₂O,(NH₄)₂SO₄.12H₂O; KAl(SO₄)₂.12H₂O, Na₂SiO₃.9H₂O, Mg(NO₂)₂.6H₂O,Na₂CO₃.7H₂O and mixtures thereof (EPI 069172A).

Aluminum hydroxide, aluminum hydroxide hydrates, magnesium hydroxide,and zinc borate are particularly preferred, since they have anactivation temperature below 180° C.

Optionally, one or more reactive flame retardants can be added to thecomposition according to the invention. Such compounds are built intothe binder. An example in the sense of the invention are reactiveorganophosphorus compounds, such as 9,10-dihydro-9-oxa-10-phosphapheneanthrene-10-oxide (DOPO) and its derivatives and adducts. Such compoundsare described, for example, in S. V. Levchik, E. D. Weil, Polym. Int.2004, 53, 1901-1929 or E. D. Weil, S. V. Levchik (eds.), FlameRetardants for Plastics and Textiles—Practical Applications, Hanser,2009.

The fire-protection additive having an ablative effect can be containedin the composition in an amount of 5 to 99 wt.-%, wherein the amountdepends essentially on the application form of the composition(spraying, brushing, and the like). In order to achieve the bestpossible insulation, the proportion of Constituent C in the totalformulation is set to be as high as possible. Preferably, the proportionof Constituent C in the total formulation amounts to 5 to 85 wt.-% and,particularly preferably, to 40 to 80 wt.-%.

Aside from the fire-protection additives that have an ablative effect,the composition can contain usual aids, if necessary, such as wettingagents, for example on the basis of polyacrylates and/or polyphosphates,anti-foaming agents such as silicone anti-foaming agents, thickenerssuch as alginate thickeners, pigments, fungicides, softening agents suchas waxes containing chlorine, binders, flame retardants or variousfillers such as vermiculite, inorganic fibers, quartz sand, micro-glassbeads, mica, silicon dioxide, mineral wool, and the like.

Additional additives such as thickeners, rheology additives, and fillerscan be added to the composition. Preferably, polyhydroxycarboxylic acidamides, urea derivatives, salts of unsaturated carboxylic acid esters,alkylammonium salts of acidic phosphoric acid derivatives, ketoximes,amine salts of p-toluene sulfonic acid, amine salts of sulfonic acidderivatives, as well as aqueous or organic solutions or mixtures of thecompounds are used are used as rheology additives, such as anti-settlingagents, anti-sag agents, and thixotroping agents. In addition, rheologyadditives on the basis of pyrogenic or precipitated silicic acid or onthe basis of silanized pyrogenic or precipitated silicic acids can beused. Preferably, the rheology additive involves pyrogenic silicicacids, modified and non-modified phyllosilicates, precipitation silicicacids, cellulose ethers, polysaccharides, PU and acrylate thickeners,urea derivatives, castor oil derivatives, polyamides and fatty acidamides and polyolefins, if they are present in solid form, powderedcelluloses and/or suspension agents such as xanthan gum, for example.

The composition according to the invention can be packaged as atwo-component or multi-component system.

If Constituent A and Constituent B do not react with one another withoutthe use of a catalyst (Constituent D) at room temperature, they can bestored together. If a reaction occurs at room temperature, Constituent Aand Constituent B must be disposed separately, so as to inhibit areaction. In the presence of a catalyst, the latter must be storedseparately from Constituent B. If, based on the nature of the catalyst,the latter reacts with Constituent A, it must be stored separately fromthe two components. A person skilled in the art recognizes or can easilydetermine which catalyst is suitable for resulting in a component thatcan be stored together with Constituent A. In general, it is importantthat Constituents A and B of the binder and the catalyst are mixed withone another only immediately before use, and then trigger the hardeningreaction.

In this connection, Constituent C can be contained as a total mixture ordivided up into individual components, in one component or multiplecomponents. The division of Constituent C takes place as a function ofthe compatibility of the compounds contained in the composition, so thatneither a reaction of the compounds contained in the composition withone another nor reciprocal disruption can take place. This is dependenton the compounds used. In this way, it is ensured that the greatestpossible proportion of fillers can be achieved. This leads to goodcooling, even at low layer thicknesses of the composition.

The composition is applied as a paste, using a brush, a roller or byspraying it onto the substrate. In this regard, the substrate can bemetallic or can consist of another, non-metallic material, such asplastic, for example, in the case of cables, or mineral wool in the caseof soft fittings, or of a material combination, for example of metallicand non-metallic materials, as in the case of cable runs. Preferably,the composition is applied by means of an airless spraying method.

The composition according to the invention is characterized, as comparedwith the solvent-based and water-based systems, by relatively fasthardening by means of an addition reaction, and thereby physical dryingis not necessary. This is particularly important if the coatedcomponents must quickly be subjected to stress or processed further,whether by being coated with a cover layer or by moving or transportingthe components. Also, the coating is therefore clearly less susceptibleto external influences on the construction site, such as, for example,an impact of (rain) water or dust and dirt, which can lead towater-soluble constituents being washed out, in solvent-based orwater-based systems, or can lead to a reduced ablative effect if dust ispicked up. Because of the low viscosity of the composition, in spite ofthe high proportion of solids, which can amount to as much as 99 wt.-%in the composition, without the addition of volatile solvents, thecomposition remains easy to process, particularly by means of commonspray methods.

For this reason, the composition according to the invention isparticularly suitable as a fire-protection coating, particularly asprayable coating for components on a metallic and non-metallic basis.The composition according to the invention is used, above all, in theconstruction sector, as a coating, particularly a fire-protectioncoating for individual cables, cable bundles, cable runs and cable ductsor other lines, as well as a fire-protection coating for steelconstruction elements, but also for construction elements composed ofother materials, such as concrete or wood.

A further object of the invention is therefore the use of thecomposition according to the invention as a coating, particularly as acoating for construction elements or components composed of steel,concrete, wood, and other materials, such as plastics, for example,particularly as a fire-protection coating for individual cables, cablebundles, cable runs, and cable ducts or other lines or soft fittings.

The present invention also relates to objects that are obtained when thecomposition according to the invention has hardened. The objects haveexcellent ablative properties.

The following examples serve to further explain the invention.

Exemplary Embodiments

The constituents listed below are used for the production ofcompositions according to the invention, having an ablative effect. Ineach instance, the individual components are mixed and homogenized usinga dissolver. For use, these mixtures are then mixed either before beingsprayed or during spraying, and applied.

To determine the fire-protection properties, the hardened compositionwas subjected to a test according to EN ISO 11925-2. The test takesplace in a burn box set up to be draft-free, a Mitsubishi FR-D700SCElectric Inverter. During the test, a small burner flame is directed atthe sample surface at an angle of 45° for 30 s; this corresponds tosurface flame exposure.

In each instance, samples having the dimensions 11 cm x 29.5 cm and ause thickness of 1 mm are used. These samples hardened at roomtemperature and were aged at 40° C. for three days.

After aging for three days at 40° C., the test for flammability and theheight of the attacked surface takes place.

The hardening time and the hardening progression were determined. Inthis connection, testing was done with a spatula to determine whenhardening of the coating starts.

For the following Examples 1 to 3, aluminum trihydrate (HN 434 from J.M. Huber Corporation, Finland) was used as Constituent C, wherein 18 gof it were used, in each instance.

EXAMPLE 1

Constituent Amount [g] Trimethylolpropane 25.9 triacrylate Trimethylphosphine 0.3 Trimethylolpropane 33.8 triacetoacetate Calcium carbonate71.1

EXAMPLE 2

Constituent Amount [g] Glycerin propoxylate 29.7 triacrylateTrimethylolpropane 26.8 triacetoacetate Potassium carbonate 3.6 Calciumcarbonate 72.0

EXAMPLE 3

Constituent Amount [g] Trimethylolpropane 12.3 triacrylate Ethyleneglycol 12.3 methacrylate Trimethylolpropane 32.0 triacetoacetatePotassium carbonate 3.4 Calcium carbonate 72.5

COMPARATIVE EXAMPLE 1

A commercial fire-protection product (Hilti CFP SP-WB) based on anaqueous dispersion technology served as a comparison.

TABLE 1 Results of the determination of hardening time, igniting, andflame height Example Comparison 1 1 2 3 Hardening 24 h  <1 h  <1 h  <1h  time Igniting yes no no no Flame height 150 mm 86 mm 65 mm 62 mm

1. A fire-protection composition, having comprising: A) a constituent A,which contains a multi-functional Michael acceptor, which has at leasttwo low-electron multiple carbon bonds per molecule as functionalMichael acceptor groups; having B) a constituent B, which contains amulti-functional Michael donor, which has at least two C-H-acidic groupsper molecule as functional Michael donor groups; C) a constituent C,which contains at least one fire-protection additive having an ablativeeffect; and having D) a catalyst for Michael addition reaction asconstituent D.
 2. The composition according to claim 1, wherein thefunctional Michael acceptor groups have the structure (I) or (II):

wherein R¹, R² and R³, independently of one another, in each instance,represent a linear, branched or cyclic, optionally substituted alkylgroup, aryl group, aralkyl group or alkyl aryl group, wherein R¹, R² andR³, independently of one another, can further contain additional anether group, a carboxyl group, a carbonyl group, a thiol-analog group, agroup containing nitrogen or a combination thereof; X represents O, S orNR⁴, in which R⁴ represents hydrogen or each of the organic groups, asthey are described for R¹, R² and R³; and Y represents OR⁵, SR⁵ orNR⁵R⁶, in which R⁵ and R⁶ represent hydrogen or each of the organicgroups as described above for R¹, R² and R3.
 3. The compositionaccording to claim 2, wherein each functional Michael acceptor group isdirectly attached to another functional Michael acceptor group, whichcan be the same or different, or to a framework, by way of one or moreof R¹, R², R³, R⁴, R⁵ or R⁶.
 4. The composition according to claim 3,wherein the functional Michael acceptor groups are bound to a polyolcompound, an oligomer or polymer by way of R⁴, R⁵ or R⁶.
 5. Thecomposition according to claim 1, wherein the functional Michael donorgroups are selected from the group consisting of β-ketoesters,β-ketoamides, 1,3-diketones, malonic esters, malonic ester derivatives,cyanoacetate esters, cyanoacetamides, α-nitroalkanes and combinationsthereof.
 6. The composition according to claim 4, wherein the functionalMichael acceptor groups or the functional Michael donor groups,independently of one another, in each instance, are bound to a polyolcompound, which is selected from the group consisting ofpentaerythritol, neopentyl glycol, glycerol, trimethylolpropane,ethylene glycol, and polyethylene glycols, propylene glycols andpolypropylene glycols, butane diol, pentane diol, hexane diol,tricyclodecane dimethylol, 2,2,4-trimethyl-1,3-pentane diol, bisphenolA, cyclohexane dimethanol, alkoxylated and/or propoxylated derivativesof neopentyl glycol and tetraethylene glycol and mixtures thereof. 7.The composition according to claim 1, wherein the reactive equivalentratio lies in the range of 0.1:1 to 10:1.
 8. The composition accordingto claim 1, wherein the at least one fire-protection additive having anablative effect is selected from the group consisting of LiNO₃.3H₂O,Na₂CO₃H₂O (thermonatrite), Na₂CO₃.7H₂O, Na₂CO₃.10H₂O (soda),Na₂Ca(CO₃)₂.2H₂O (pirssonite), Na₂Ca(CO₃)₂.5H₂O (gaylussite),Na(HCO₃)Na₂CO₃.2H₂O (trona), Na₂S₂O₃.5H₂O, Na₂O₃Si.5H₂O, KF.2H₂O,CaBr₂.2H₂O, CaBr₂.6H₂O, CaSO₄.2H₂O (gypsum), Ca(SO₄).½H₂O (bassanite),Ba(OH)₂.8H₂O, Ni(NO₃)₂.6H₂O, Ni(NO₃)₂.4H₂O, Ni(NO₃)2.2H₂O,Zn(NO₃)₂.4H₂O, Zn(NO₃)₂.6H₂O, (Zn0)₂(B₂O₃)₂.3H₂O, Mg(NO₃)₂.6H₂O (U.S.Pat. No. 5,985,013 A), MgSO₄.7H₂O (EP1069172A), Mg(OH)₂, Al(OH)₃,Al(OH)₃.3H₂O, AlOOH (boehmite), Al₂[SO₄]₃.nH₂O with n=14-18 (U.S. Pat.NO. 4,462,831 B), optionally in a mixture with AINH₄(SO₄)₂.12H₂O (U.S.Pat. No. 5,104,917A), K AI(SO₄)₂.12H₂O (EP1069172A), CaO.Al₂O₃.10H₂O(nesquehonite), MgCO₃.3H₂O (wermlandite), Ca₂Mg₁₄(Al,Fe)₄CO₃(OH)₄₂.29H₂O(thaumasite), Ca₃Si(OH)₆(SO₄)(CO₃).12H₂O (artinite), Mg₂(OH)₂CO₃.H₂O(ettringite), 3CaO.Al₂O₃.3CaSO₄.32H₂O (hydromagnesite),Mg₅(OH)₂(CO₃)₄.4H₂O (hydrocalumite), Ca₄Al₂(OH)₁₄.6H₂O (hydrotalcite),Mg₆Al₂(OH)₁₆CO₃.4H₂O alumohydrocalcite, CaAl₂(OH)₄(CO₃)₂.3H₂Oscarbroite, Al₁₄(CO₃)₃(OH)₃₆ hydrogarnet, 3CaO.Al₂O₃.6H₂O dawsonite,NaAl(OH)CO₃, aqueous zeolite, vermiculite, colemanite, perlites, mica,alkali silicates, borax, modified carbons, graphites, silicic acids, andmixtures thereof.
 9. The composition according to claim 1, furthercomprising an organic and/or inorganic admixture and/or anotheradditive.
 10. The composition according to claim 1, which is packaged asa two-component or multi-component system.
 11. A coating, comprising:the composition according to claim
 1. 12. A construction element,comprising: the coating according to claim
 1. 13. A non-metalliccomponent, comprising: the coating according to claim
 1. 14. The coatingaccording to claim 11 which comprises a fire-protection layer.
 15. Ahardened object obtained by hardening the composition according toclaim
 1. 16. A method of producing a coating, comprising: coating asurface with the composition according to claim 1.